Method of producing alcohols

ABSTRACT

A method of making alcohols involves forming of alcohol esters from liquid alkane halides and a solution of metallic salts of organic acids to produce gaseous alcohol esters for reaction with magnesium or metal hydroxides to form the alcohol and the metal salt of the organic acids. In an improvement method liquid phase alcohol esters instead of gaseous alcohol esters are produced from liquid alkane halides and a solution of metal salts of organic acids whose alkane esters are less soluble in water than that of the alkane halide and treating of the alcohol ester formed with magnesium or metal hydroxides to form the alcohol and the metal salt of the organic acids.

RELATED APPLICATIONS

This application claims priority to U.S. application Ser. No. 12/927,936filed Nov. 30, 2010, which claims priority to U.S. ProvisionalApplication Nos. 61/283,167 filed on Nov. 30, 2009; and 61/336,962,filed on Jan. 28, 2010, the disclosures of which are each incorporatedherein by reference.

TECHNICAL FIELD

The disclosure relates to a method of making alcohols, and morespecifically alkanols, from alkanes, and more specifically from alkanehalides.

BACKGROUND

Alcohols are industrially produced from direct hydration of alkenes,such as ethylene, or from cracking of appropriate fractions of distilled(or fractionated) crude oil. While demands for alcohols, and especiallyfor ethanol, continue to increase, crude oil reserves continue to bedepleted. Moreover, the processes of alkene hydration and fractionationand cracking of crude oil are themselves energy intensive processes.

There remains a need therefore, for a method of producing alcohols frommore readily available starting materials and for a process which doesnot require the energy input necessary for current industrial alcoholproduction.

SUMMARY OF THE DISCLOSURE

The disclosure provides a method of making alcohols. More specifically,an illustrative disclosed method comprises reacting an alkane gas with ahalogen gas in a halogenation reactor to form a halogenation reactionproduct mixture comprising alkane halide and hydrogen halide mixture;contacting the halogenation reaction product mixture with a metalorganic salt thereby forming an extractor product mixture of a metalhalide, organic ester, and organic acid; separating the organic esterand organic acid mixture from the metal halide; oxygenating the metalhalide to form a metal oxide and halide containing gasses; separatingthe metal oxide from the halide containing gasses; mixing the metaloxide with water to form a metal oxide slurry; mixing the metal oxideslurry with a countercurrent flow of the organic ester and organic acidmixture to form a raw product comprising alkanol and a metal organicsalt.

In an improvement method of making alcohols, the disclosed methodinvolves liquid phase forming of alcohol esters from liquid alkanehalides and a solution of metal salts of organic acids whose alkanesesters are less soluble in water than that of the alkane halide andtreating of the alcohol ester formed with magnesium or metal hydroxidesto form the alcohol and the metal salt of the organic acids.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings illustrate an exemplary form of the disclosure; it beingunderstood, however, that this disclosure is not limited to the precisearrangements and instrumentalities shown in the drawing.

FIG. 1 is a schematic diagram of one embodiment of the disclosedprocess.

FIG. 2 is a schematic diagram of an alternative illustrative method ofthe disclosed process.

FIG. 3 is a schematic diagram of another aspect of the method of thedisclosed process.

DETAILED DESCRIPTION

The disclosure is a method for making alcohols. The disclosure is amethod for producing organic alcohols, including for example, methanol,ethanol, propanol, and combinations thereof.

In one illustrative embodiment, the instant disclosure provides a methodcomprising: reacting an alkane with a halogen gas in a halogenationsreactor to form a halogenation reaction product mixture comprisingalkane halide and hydrogen halide mixture; contacting the halogenationreaction product mixture with a metal organic salt thereby forming anextractor product mixture of a metal halide, organic salt, organicester, and organic acid; separating the organic ester and organic acidmixture from the metal halide; oxygenating the metal halide to form ametal oxide and halide containing gasses; separating the metal oxidefrom the halide containing gasses; mixing the metal oxide with water toform a metal oxide slurry; mixing the metal oxide slurry with acountercurrent flow of the organic ester and organic acid mixture toform a raw product comprising alkanol and a metal organic salt.

In an alternative illustrative improvement embodiment, the instantdisclosure provides a method comprising: reacting an alkane with ahalogen gas in a halogenations reactor to form a halogenation reactionproduct mixture comprising alkane halide and hydrogen halide mixture;contacting the halogenation reaction product mixture with a metalorganic salt under aqueous conditions thereby forming an aqueousextractor product mixture of a soluble metal halide, and an insolubleorganic ester; separating the insoluble organic ester from the aqueousmetal halide; oxygenating the metal halide to form a metal oxide andhalide containing gasses; separating the metal oxide from the halidecontaining gasses; mixing the metal oxide with water to form a metaloxide slurry; mixing the metal oxide slurry with a countercurrent flowof the insoluble organic ester and insoluble organic salt mixture toform a raw product comprising alkanol.

In yet another alternative illustrative improvement method of makingalcohols, the instant disclosure provides a method for the production ofalcohols comprising: contacting an alkane gas with an aqueous halidesaturated solution to strip the halide from the solution to form aproduct mixture of an alkane and a halide; reacting a halogen gas withthe alkane halide mixture to form an alkyl halide, an alkyl di halide,an alkyl tri halide, and a hydrogen halide gasses; neutralizing thealkyl di halide, the alkyl tri halide, and the hydrogen halide gasseswith a suspension of magnesium hydroxide; cooling the gasses from theneutralizing step to a temperature to liquefy the gasses to formliquefied gasses; mixing the liquefied gasses with a magnesium benzoateor butyrate solution to form an aqueous solution of benzoate or butyrateethyl esters; separating the benzoate or butyrate ethyl esters in theaqueous solution which are water insoluble from water in the aqueoussolution to form an ester insoluble layer comprising benzoate orbutyrate ethyl esters and a water layer containing magnesium halide;contacting the ester insoluble layer with a suspension of magnesiumhydroxide to form an alcohol.

Alkanes useful in various embodiments of the disclosed methods may beselected from the group consisting of C1-C20 alkanes, including mostpreferably, methane, ethane, propane, butane and mixtures thereof. Allcombinations and subcombinations of such alkanes are included anddisclosed herein. For example, the alkanes may comprise a mixture ofmethane and ethane; or in the alternative, a mixture of methane andpropane; or in the alternative, a mixture of ethane and butane. In thealternative, the alkane may comprise only a single alkane. For example,the alkane may comprise methane with no other alkane component; or inthe alternative, the alkane may comprise ethane with no other alkanecomponent; or in the alternative the alkane may comprise propane with noother alkane component.

Halogen gasses useful in various embodiments of the disclosed methodsmay be selected from the group consisting of chlorine gas, bromine gas,iodine gas, and combinations thereof. All combinations andsubcombinations of such halogen gasses are included and disclosedherein. For example, the halogen gasses may comprise a mixture ofchlorine and bromine gasses; or in the alternative the halogen gassesmay comprise a mixture of chlorine and iodine gasses. In thealternative, the halogen gas useful in the halogenations step of thedisclosed method may comprise only a single halogen gas. For example thehalogen gas may be bromine gas; or in the alternative, the halogen gasmay be chlorine gas. The halogen gas or gasses used in the halogenationreactor may be supplied directly into the halogenations reactor, as forexample, by injection through a dedicated supply line. Alternatively,the halogen gas or gasses used in the halogenation reactor may be formedin situ in the halogenation reactor.

Metal organic salts useful in the disclosed method of FIG. 1 may beselected from the group consisting of metal formate, metal acetate,metal benzoate, and combinations thereof. The metal of the metal organicsalt in various embodiments of the disclosed method of FIG. 1 may beselected from Magnesium, Zinc, and combinations thereof, for example.All combinations and subcombinations of the metal organic salts aredisclosed and included herein. For example, the metal organic salt maybe magnesium formate, zinc acetate, magnesium benzoate, zincdichlorobenzoate, zinc dichloroacetate, or any combination of two ormore of the foregoing. Metal organic salts useful in the improvementmethods disclosed below are selected based on the water solubility ofthe alkane halide with which the metal organic salt is reacted and thealkane ester product resulting from that reaction in water.Specifically, if the alkane ester product has a solubility that is lessthan the solubility of the reactant alkane halide, then the alkane esterproduct will precipitate out of the water into an insoluble layer whichcan be easily separated from the metallic halide which remains in thewater. This separation of insoluble alkane ester from the metallichalide permits the metallic halide to be processed downstreamindependent from the alkane ester stream to form the metallic hydroxiderequired to be contacted with the alkane ester to form the alkanealcohol. If, however, the alkane ester product has a solubility that isgreater than the solubility of the reactant alkane halide, the alkaneester product will not precipitate out of the water but remain with themetallic halide as a mixture in the water; making the reaction of themetallic halide into metallic hydroxide not possible. The metal organicsalt may be a magnesium benzoate or a magnesium butyrate or a magnesiumsalicylate, for example, which are the magnesium salts of benzoic acid,butyric acid, and salicyclic acid, respectivily. When magnesium butyrateis used, for example, the solubility of the ethyl bromide in water is0.91 grams per 100 ml of water, or 0.0835 moles per 1000 ml of water andthe solubility of ethyl butyrate is 0.68 grams per 100 ml of water or0.059 moles per 1000 ml. Because the solubility of the ethyl butyrate isless than the solubility of the magnesium butyrate in water, the ethylbutyrate will precipitate out of the water as an insoluble layeraccording the teachings of this disclosure. When methyl formate is used,however, the solubility of the methyl formate is greater than thesolubility of the ethyl bromide and hence the methyl formate will remainwith the ethyl bromide in the aqueous solution.

In one embodiment of the disclosed method of FIG. 1, the alkane ismethane, the metal organic salt is magnesium formate, the halide gas isbromine gas, and the alkanol is methanol.

In an alternative embodiment with all of the disclosed methods, thedisclosure provides a method of making alkanols except that the halogengas is chlorine gas.

In an alternative embodiment with all the disclosed methods, thedisclosure provides a method of making alkanols except that the halogengas is a mixture of bromine and chlorine gasses.

In an alternative embodiment with all the disclosed methods, thedisclosure provides a method of making alkanols except that the alkaneis ethane.

In an alternative embodiment with all the disclosed methods, thedisclosure provides a method of making alkanols except that the alkaneis propane.

In an alternative embodiment with all the disclosed methods, thedisclosure provides a method of making alkanols except that the alkaneis butane.

In an alternative embodiment with all the disclosed methods, thedisclosure provides a method of making alkanols except that the alkaneis a mixture of methane and ethane.

In an alternative embodiment of FIG. 1, the invention provides a methodof making alkanols except that the metal organic salt is magnesiumacetate.

In an alternative embodiment of all the disclosed methods, the inventionprovides a method of making alkanols except that the metal organic saltis magnesium benzoate.

In an alternative embodiment of all the disclosed methods, the inventionprovides a method of making alkanols except that the metal organic saltis zinc benzoate.

In an alternative embodiment of FIG. 1, the invention provides a methodof making alkanols except that the metal organic salt is magnesiumacetate. In an alternative embodiment of FIG. 1, the invention providesa method of making alkanols except that the metal organic salt is zincformate.

The various steps of the disclosed method may be conducted in anyappropriate reactor. For example, in the disclosure of both methods, thestep of oxygenating the metal halide may occur in a fluidized bedreactor, otherwise known as, a fluo-solids reactor. In some embodimentsof the disclosed method the step of contacting the halogenation reactionproduct mixture with a metal organic salt occurs in a column packed withan inert packing material. Any one or more inert materials as are knownin the art may be used in the step of contacting the halogenationsreaction product mixture with a metal organic salt may be used,including for example Berl saddles. In some embodiments of the disclosedmethods, the step of contacting the halogenation reaction productmixture with a metal organic salt solution occurs by flowing thehalogenation reaction product mixture against a countercurrent flow ofthe metal organic salt.

In some embodiments, the disclosed methods further comprises strippingthe bromine from the bromine containing gasses and recycling the bromineinto the halogenations reactor in the case of FIG. 1 and a brominatorreactor in the case of FIG. 2.

The reactors, condensers, mixers, distillation reactor, decanter, andother equipment used in the illustrative embodiments shown in the FIGS.are well known in function and operation.

In certain embodiments of the disclosed method, the alkane to halogengas molar ratio may be greater than 2:1. All individual values andsubranges greater than a 2:1 ratio are included herein and disclosedherein; for example, the alkane to halogen gas molar ration can be froma lower limit of 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.5:1, 3.8:1,4:1; 4.2:1. In at least one aspect of the present disclosure the alkaneto halogen gas molar ratio is greater than or equal to 4:1. Thehalogenations step in all the methods wherein the alkane and halogen gasare reacted to form an alkane halide and the hydrogen halide is, in someembodiments of the disclosed methods, autocatalytic followinginitiation. In such embodiments, the halogenations reaction may beinitiated by application of heat to a temperature between 350 and450.degree. C. All individual values and subranges from 350 and450.degree. C. are included herein and disclosed herein; for example,the halogenation reaction initiation temperature can be from a lowerlimit of 350, 360, 370, 380, 390, 400, 410, 420, 430, or 440.degree. C.to an upper limit of 360, 370, 380, 390, 400, 410, 420, 430, 440 or450.degree. C. For example, the halogenation reaction initiationtemperature may be in the range of from 350 to 380.degree. C., or in thealternative, halogenation reaction initiation temperature may be in therange of from 380 to 400.degree. C., or in the alternative, thehalogenation reaction initiation temperature may be in the range of from400 to 450.degree. C.

In alternative embodiments, the halogenations reaction may be initiatedat lower temperatures in the presence of ultraviolet radiation. In suchembodiments, the halogenations reaction initiation temperature may be inthe range from 250 to 350.degree. C. All individual values and subrangesfrom 250 and 350.degree. C. are included herein and disclosed herein;for example, the halogenation reaction initiation temperature can befrom a lower limit of 250, 260, 270, 280, 290, 300, 310, 320, 330, or340.degree. C. to an upper limit of 260, 270,280, 290, 300, 310, 320,330, 340 or 350.degree. C. for example, the halogenation reactioninitiation temperature may be in the range of from 250 to 280.degree.C., or in the alternative, halogenation reaction initiation temperaturemay be in the range of from 280 to 300.degree. C., or in thealternative, the halogenation reaction initiation temperature may be inthe range of from 300 to 350.degree. C.

Following initiation, in some embodiments of the disclosed method, theheat generated by the halogenation reaction is sufficient to maintainthe halogenation reaction.

The following examples and description of the drawings is an example ofone or more embodiments of the disclosed methods and is not intended tolimit the scope of the disclosure.

Examples Original Example 1

Referring to FIG. 1, natural gas comprising methane enters a mixingchamber 1 through line 2 in which it is mixed with bromine vaporentering mixing chamber 1 through line 3. The natural gas/bromine vapormixture passes into the halogenations reactor 5 wherein methyl bromideand hydrobromic acid are formed. The halogenations reaction productmixture which may further comprise unreacted gasses passes through line6 to condenser 7 wherein the mixture is cooled. Following cooling thehalogenation reaction product mixture is passed through line 8 andflowed upward into extractor 9 through an inert packing material 10 (notshown) against a counterflow of magnesium formate solution which entersextractor 9 through line 38. Magnesium bromide is formed and magnesiumbromide solution exits extractor 9 through line 11. Also formed inextractor 9 is methyl formate and formic acid gasses which exitextractor 9 through line 12. Magnesium bromide solution enters reactor13 wherein it is heated and reacted with oxygen entering through line16. Bromine containing gasses are led from reactor 13 through line 17 tocooler 18 where most of the bromine is recovered and exits cooler 18through line 19. Gasses containing traces of bromine are led from cooler18 to absorber 20 through line 21 wherein the gasses are contacted witha counterflow of solvent, thereby recovering the remainder of thebromine Bromine free gasses may be vented or otherwise routed throughline 22. The bromine containing solvent exits the bottom of absorber 20and enters the top of stripper 23 through line 24. In the stripper 23,the bromine containing solvent is contacted with methane entering thestripper 23 through line 39, thereby stripping the bromine from thebromine containing solvent. Stripped solvent may be recovered from thebottom of stripper 23 and pumped using pump 26 through line 28 into thetop of absorber 20. Magnesium oxide from oxidation reactor 13 enterreactor 29 through line 30. Water is added to reactor 29 through line31. A slurry of magnesium oxide is formed in reactor 29 and is passedthrough line 32 into the top of stripper 33 wherein the magnesium oxideslurry is contacted with a counterflow of methyl formate and formic acidgasses. In stripper 33, methanol is formed and exits stripper 33 tocondenser 34. Condenser 34 cools the methanol which is collected throughline 35. Gas products of stripper 33 which are substantially free ofmethanol are passed into mixing chamber 1 through line 36. Magnesiumformate solution leaves stripper 33 through line 38 through which it ispassed into extractor 9.

Advantageously, the magnesium bromide, the liquid metallic halide inline 11 is separated from the liquid methyl formate, the alkane ester,under gaseous conditions in extractor 9 in Example 1 as follows:

Metallic Formate (l)+Methyl Bromide (l)→Methyl Formate (g)+MagnesiumBromide (l)  (1)

In other words, the following is the condition for the separation of thealkane ester from the alkane halide in a reaction:

Metallic Organic Salt (l)+Alkane Halide (l)→Alkane Ester (g)+MetallicHalide (l)  (2)

which allows for the processing of the liquid magnesium bromide byoxidation reactor 13 and reactor 29 for the formation of the slurry ofmagnesium oxide found in line 6 required to form the methyl alkanol.More specifically, the alcohol is formed by reaction of the liquidmagnesium hydroxide, the liquid metallic hydroxide in line 6, and methylformate gas, the alkane ester gas in line 12 to form the liquid metallicsalt, the metal ester in line 38, and the methanol gas, the alkanealcohol that enter condenser 34 for condensation and recover as follows:

Methyl Formate (g)+Magnesium Hyrdoxide (l)→Methanol (g)+MagnesiumFormate (l)  (3)

Improvement Examples

In the Improvement Examples, at the point where the alkane esters areformed from the reaction of the liquid alkane halide and the metallicorganic salt in accordance with chemical equation 3 above, the reactionadvantageously occurs under conditions such that the alkane estersformed are insoluble in the aqueous solution containing the liquidalkane halides and the liquid metal organic salt as the reactants. Thisallows for the separation of the liquid alkane esters from the liquidmetallic halide so that the liquid metallic halide can be furtherprocessed into the slurry of metallic oxides that may be reacted withthe liquid ester to form the alkane alcohol. Advantageously, the alkanehalides that are contacted with the metallic organic salt in theImprovement Examples are selected such that the alkane esters formedfrom the reaction of the alkane halide and the metallic organic salthave a solubility in water that is less than the solubility of thealkane halide in water. If the alkane ester product has a solubilitythat is less than the solubility of the reactant alkane halide, then thealkane ester product will precipitate out of the water into an insolublelayer which can be easily separated from the metallic halide whichremains in the water. This separation of insoluble alkane ester from themetallic halide permits the metallic halide to be processed downstreamindependent from the alkane ester stream to form the metallic hydroxiderequired to be contacted with the alkane ester to form the alkaneethanol. If, however, the alkane ester product has a solubility that isgreater than the solubility of the reactant alkane halide, the alkaneester product will not precipitate out of the water but remain with themetallic halide as a mixture in the water; making the reaction of themetallic halide into metallic hydroxide not possible.

Improvement Example 1

Improvement Example 1 uses the same process and equipment as shown inFIG. 1 except that equipment 9 which is an extractor in the Example 1 isreplaced with a separator in Example 2 for the purpose of separatingalkane esters from metal halides in the mix of products that is formedin the separator. As previously discussed, the alkane esters inImprovement Example 1 are formed from the reaction of the liquid alkanehalide and the metallic organic salt, such that the reactionadvantageously occurs under conditions such that the alkane estersformed are insoluble in the aqueous solution containing the liquidalkane halides and the liquid metal organic salt as the reactants. Morespecifically, the alkane esters formed in separator 9 in ImprovementExample 1 are chosen to have a solubility in water that is less than thesolubility of the alkane halide in water.

In other words, the following is the condition for the separation of thealkane ester from the alkane halide in a reaction in Improvement Example1:

Metallic Organic Salt (l)+Alkane Halide (l)→Alkane Ester (l)+MetallicHalide (l)  (4)

As seen in chemical equation 4, the alkane ester remains as a liquid inthe product mix in this reaction. In Improvement Example 1, an ethylbutyrate is used as the alkane ester. From chemical reaction 4, inImprovement Example 1, ethyl bromide is the alkane halide of choice asthe alkane halide for use as a reactant to the metallic organic saltaccording to the following reaction occurring in separator 9:

Metallic Butyrate (l)+Ethyl Bromide (l)→Ethyl Butyrate (l)+MagnesiumBromide (l)  (5)

This is because the solubility of the ethyl bromide (i.e., which reactswith the metallic organic salt to form the alkane ester according tochemical equation 5 above) in water is 0.91 grams per 100 ml of water,or 0.0835 moles per 1000 ml of water which is greater than thesolubility of ethyl butyrate in water which is 0.68 grams per 100 ml ofwater or 0.059 moles per 1000 ml. In other words, the solubility of theethyl butyrate (i.e., the alkane ester) in water is less than thesolubility of its reactant ethyl bromide (i.e., its alkane halidereactant) in water. This advantageously keeps the ethyl butyrate in aliquid phase in separator 9. Since liquid ethyl butyrate is insoluble inwater, the liquid ethyl butyrate advantageously forms an insoluble layerwith the aqueous magnesium bromide solution layer. This allows theliquid ethyl butyrate to be advantageously separated in separator 9 fromthe magnesium bromide solution which allows the magnesium bromidesolution to be processed into the magnesium oxide slurry in line 32required for reaction with the liquid ethyl butyrate in line 12 to formthe ethanol in stripper 33.

Improvement Example 2

In Improvement Example 2, an methyl benzoate is used as the alkaneester. As in Improvement Example 1, ethyl methyl benzoate is chosen asthe alkane halide for use as a reactant to the metallic organic saltaccording to the following reaction occurring in separator 9:

Metallic Benzoate (l)+Methyl Bromide (l)→Methyl Benzoate (l)+MagnesiumBromide (l)  (6)

This is because the solubility of methyl bromide (i.e., which reactswith the metallic organic salt to form the alkane ester according tochemical equation 6 above) in water is 0.09 grams per 100 ml of water,or 0.0094 moles per 1000 ml of water which is greater than thesolubility of methyl benzoate in water which is 0.157 grams per 100 mlof water or 0.0011532 moles per 1000 ml. In other words, the solubilityof the methyl benzoate (i.e., the alkane ester) in water is less thanthe solubility of its reactant methyl bromide (i.e., its alkane halidereactant) in water. This advantageously keeps the methyl benzoate in aliquid phase in separator 9. Since liquid methyl benzoate is insolublein water, the liquid methyl benzoate advantageously forms an insolublelayer with the aqueous magnesium bromide solution. This allows theliquid methyl benzoate to be advantageously separated in separator 9from the magnesium bromide solution which allows the magnesium bromidesolution to be processed into the magnesium oxide slurry in line 32required for reaction with the liquid methyl benzoate in line 12 to formthe methanol in stripper 33.

Improvement Example 3

In Improvement Example 3, a methyl formate is used as the alkane ester.In this Improvement Example 3, the methyl formate is quickly seen to bean unworkable choice since the methyl halide for use as a reactant tothe metallic organic salt does not follow the following reactionrequired to keep the alkane ester as a liquid in separator 9 accordingto the following teachings of my improvement disclosure:

Metallic organic salt (l)+Alkane Halide (l)→Alkane Ester (l)+MetallicHalide (l)  (7)

This is because the solubility of methyl bromide (i.e., which reactswith the metallic organic salt to form the alkane ester according) inwater is 0.09 grams per 100 ml of water, or 0.0094 moles per 1000 ml ofwater which is less than the solubility of methyl formate in water whichis 30.4 grams per 100 ml of water or 5.0624479 moles per 1000 ml. Inother words, the solubility of the methyl formate (i.e., the alkaneester) in water is greater than the solubility of its reactant methylhalide (i.e., its alkane halide reactant) in water. As a result, themethyl formate remains in the aqueous metal hydroxide solution in liquidseparator 9 as a solvent which prevents the magnesium bromide solutionto be processed into the magnesium oxide slurry in line 32 required forreaction to form the methanol. In other words, because the solubility ofthe methyl formate was not less than the solubility of its reactantmethyl bromide, there is no methyl formate product in line 12 for use informing the methanol in stripper 33. In contradistinction, in Example 1,there was a gaseous methyl formate product formed in line 12 for use inthe methanol production reaction in stripper 33 because the extractor 9evaporates the methyl formate from the magnesium bromide solution tocreate the required separation between the magnesium bromide and themethyl formate in extractor 9.

Improvement Example 4

Referring to FIG. 2, bromine is produced in fluo-solids reactor 1. Thebromine vapor passes through line 3 to condenser 2 where most of thebromine, typically up to about 95%, for example, may be is condensed.The uncondensed bromine vapor passes through line 5 to absorber 4 and isflowed against a counterflow of water. Clean gasses from the cross-floware vented to the atmosphere through line 6. Water saturated withbromine forming an aqueous bromine saturated solution passes throughline 8 to extractor 7. In extractor 7, the aqueous bromine saturatedsolution flows against a counterflow of ethane gas which strips all, orsubstantially all, of the bromine from the water. The ethane containingthe stripped bromine passes through line 9 to brominator reactor 10.Liquid bromine from condenser 2 passes through line 11 to vaporizer 12where the liquid bromine is vaporized and preheated before passingthrough line 13 to brominator reactor 10. Bromine and ethane inbrominator reactor 10 react to form ethyl bromide, ethyl dibromide,ethyl tri bromide, and hydrogen bromide gasses. These gasses exitingreactor 10 pass through line 15 to neutralizing reactor 14 where ethyldi-bromide, ethyl tri-bromide, and hydrogen bromide are neutralized witha suspension of magnesium hydroxide flowing through line 19 from reactor18. Liquids from neutralizing reactor 14 pass through line 32 to fluosolids reactor 1. Gasses from neutralizing reactor 14 pass through line20 to condenser 12 where the gasses are cooled.

These gases are cooled to temperatures below and preferably well belowthe boiling point of ethyl bromide. Liquid products from condenser 21pass through line 22 to intensive mixer 23, which also receivesmagnesium benzoate or butyrate solution from reactor 29 through line 40.The liquid product from intensive mixer 23 passes through line 26 todecanter 27 where benzoate or butyrate ethyl esters separate as asubstantially insoluble ester layer (phase 2 liquid) from the waterlayer (phase 1 liquid). The water layer containing magnesium bromide, orphase 1 liquid, flows out of decanter 27 along line 36 to reactor 1. Theinsoluble ester layer containing benzoate or butyrate ethyl esters, orphase 2 liquid, flows out of decanter 27 through line 28 to distillationreactor 29. At distillation reactor 29, the phase 2 insoluble esterlayer contacts a suspension of magnesium hydroxide which entersdistillation reactor 29 through line 41 from reactor 18. Alcohol(ethanol) from distillation reactor 29 is recovered as product throughline 31. Solid product from fluo-solid reactor 1, containing magnesiumoxide, flows through line 42 to reactor 18 where it contacts waterentering reactor 18 from line 34 and reacts to form magnesium hydroxide.Magnesium hydroxide flows from reactor 18 to brominator reactor 10 anddistillation reactor 29.

Advantageously, the alkane halides that are contacted with the metallicorganic salt in intensive mixer 23 are selected such that the alkaneesters formed in intensive mixer 23 have a solubility in water that isless than the solubility of the alkane halide in water. If the alkaneester product has a solubility that is less than the solubility of thereactant alkane halide, then the alkane ester product will precipitateout of the water into an insoluble layer which can be easily separatedfrom the metallic halide which remains in the water. This separation ofinsoluble alkane ester from the metallic halide permits the metallichalide to be processed downstream independent from the alkane esterstream to form the metallic hydroxide required to be contacted with thealkane ester to form the alkane alcohol. If, however, the alkane esterproduct has a solubility that is greater than the solubility of thereactant alkane halide, the alkane ester product will not precipitateout of the water but remain with the metallic halide as a mixture in thewater; making the reaction of the metallic halide into metallichydroxide not possible. Hence, unlike Example 1 where the organic estergoing to stripper 33 on line 12 is a gas, the organic ester flowing online 28 in Example 3 from decanter 27 to distillation reactor 29 is aliquid; just as the organic ester flowing into stripper 33 on line 12 inExample 2 is a liquid. The liquid organic ester may enable the use ofsmaller equipment in the process, eliminate the need for a gas pump,have lower energy requirements, be less expensive and produce morealcohol output per unit volume than is possible using the method ofExample 1.

Improvement Example 5

An illustrative alternative method for the production of alcohols isshown in FIG. 3 and includes the steps of reacting:

1. producing a halogen gas in a fluo -solids reactor 101, solidscomprising a metal and a halogen forms a halogen gas and a metal oxide;

2. condensing the halogen gas in a condenser 102, forming a liquidhalogen and a gas comprising trace halogen, the liquid halogen may bevaporized in vaporizer 112 and fed to a brominator 110;

3. recovering the trace halogen from the gas by absorbing the tracehalogen in water, in absorber 104;

4. contacting an alkane to the absorbed trace halogen and water andforming a gas comprising the alkane and trace halogen (e.g. gas with anaqueous halide saturated solution), in extractor 107;

5. stripping the trace halogen from the solution to form a productmixture of an alkane and a halide;

6. feeding the product mixture of an alkane and a halide to brominator110;

7. reacting the halogen and the alkane in brominator 110 to formhalogenated alkanes;

8. reacting the metal oxide, formed in fluo solids reactor 101, withwater forming a metal hydroxide in reactor 118;

9. feeding a portion of the metal hydroxide to a neutralizer 114;

10. neutralizing at least a portion of the halogenated alkanes with themetal hydroxide, forming neutralized gasses and liquids in neutralizer114;

11. feeding the neutralized liquids to fluo solids reactor 101;

12. condensing a portion of the neutralized gasses in condenser 121forming a condensate and a gas;

13. feeding the gas from condenser 121 to brominator reactor 110;

14. feeding the condensate from condenser 121 to intensive mixer 123;

15. mixing, in intensive mixer 123, the condensate from condenser 121with metallic organic salt, fed from distiller/reactor 129, forming areacted liquid;

16. decanting the reacted liquid into a first liquid phase and a secondliquid phase in decanter 127 wherein the first liquid phase comprises ametal halogen and water and is fed to fluo solids reactor 101;

17. feeding the second liquid phase to distiller/reactor 129 wherein thesecond liquid may comprise metal hydroxide;

18. distilling and reacting of the second liquid phase indistiller/reactor 129, removing alcohol therefrom; and

19. removing the metal benzoate or butyrate from distiller/reactor 129and feeding to the intensive mixer 123.

In at least one aspect of the process shown in FIG. 3, the metalscomprised in the solids fed to fluo solids reactor 101 comprisesmagnesium. In this aspect the metal oxide fed to reactor 118 from fluosolids reactor 101 comprises MgO. The metal hydroxide fed to neutralizer114 and distiller/reactor 129, from reactor 118, comprises MgOH.Additionally, the metal benzoate or butyrate fed from distiller/reactor129 comprises magnesium benzoate or butyrate.

In at least one additional aspect of the process shown in FIG. 3, thehalogens comprised in the solids fed to fluo solids reactor 101comprises bromine In this aspect of the process, the halogens fed tobrominator 110 comprise bromine. In at least further aspect of theprocess shown in FIG. 3, the alkane fed to extractor 107 comprisesethane. In this aspect, the halogen and alkane fed to brominator 110,from extractor 107, comprises ethane. In yet another aspect of theprocess shown in FIG. 3, the halogens comprised in the solids fed tofluo solids reactor 101 comprises bromine and the metals comprised inthe solids fed to fluo solids reactor 101 comprises magnesium. In thisaspect, the phase 1 liquid fed to fluo solids reactor 101, from decanter127, comprises MgBr₂.

As with the other Improvement Examples, the method disclosed inconnection with Improvement Example 5 involves liquid phase forming ofalcohol esters from liquid alkane halides and a solution of metal saltsof organic acids whose alkanes esters are less soluble in water thanthat of the alkane halide and treating of the alcohol ester formed withmagnesium or metal hydroxides to form the alcohol and the metal salt ofthe organic acids.

From all of the examples above and the entirety of this disclosure, thefollowing can be seen. A method of making alcohols may involve formingof alcohol esters from liquid alkane halides and a solution of metallicsalts of organic acids to produce gaseous alcohol esters for reactionwith magnesium or metal hydroxides to form the alcohol and the metalsalt of the organic acids. In an improvement method, liquid phasealcohol esters instead of gaseous alcohol esters are produced fromliquid alkane halides and a solution of metal salts of organic acidswhose alkane esters are less soluble in water than that of the alkanehalide and treating of the alcohol ester formed with magnesium or metalhydroxides to form the alcohol and the metal salt of the organic acids.

INDUSTRIAL APPLICABILITY

The disclosed methods have wide use for producing alcohols from morereadily available starting materials and may provide efficiencies inenergy input requirements and costs over current industrial alcoholproduction from direct hydration of alkenes, or from cracking ofappropriate fractions of distilled (or fractionated) crude oil.

More specifically, the disclosed improvement methods illustrated by theImprovement Examples in connection with FIG. 1 and the methods disclosedin connection with FIGS. 2 and 3 involve liquid phase forming of alcoholesters from liquid alkane halides and a solution of metal salts oforganic acids whose alkanes esters are less soluble in water than thatof the alkane halide and treating of the alcohol ester formed withmagnesium or metal hydroxides to form the alcohol and the metal salt ofthe organic acids. In these disclosed improvement methods, the liquidorganic ester may enable the use of smaller equipment in the process,eliminate the need for a gas pump, have lower energy requirements, beless expensive and produce more alcohol output per unit volume than ispossible using the method of Original Example 1.

The present disclosure may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the disclosure.

1. A method for the production of alcohols comprising: liquid phaseforming of alcohol esters from liquid alkane halides and a solution ofmetal salts of organic acids whose alkane esters are less soluble inwater than that of the alkane halide and treating of the alcohol esterformed with magnesium or metal hydroxides to form the alcohol and themetal salt of the organic acids.
 2. The method of claim wherein thealkane gas is selected from the group consisting of methane, ethane,propane and mixtures thereof.
 3. The method of claim 1 wherein thehalogen gas is selected from the group consisting of chlorine gas,bromine gas, and iodine gas, and mixtures thereof.
 4. The method ofclaim 1 wherein the alkane is methane, the halide gas is selected fromthe group consisting of bromine gas, chlorine gas, and mixtures thereof,and the alcohol is methanol.
 5. The method of claim 1 wherein the alkaneis ethane, the halide gas is bromine gas, and the alcohol is ethanol. 6.The method of claim 1 wherein the metal salts of organic acids isselected from the group consisting of magnesium benzoate, magnesiumbutyrate, or a magnesium salicylate.
 7. The method of claim 1 whereinthe acids are selected from the group consisting of benzoic acid,butyric acid, and salicyclic acid.
 8. The method of claim 1 wherein thealcohol is selected from the group consisting of methanol or ethanol. 9.A method for the production of alcohols comprising: contacting an alkanegas with an aqueous halide saturated solution to strip the halide fromthe solution to form a product mixture of an alkane and a halide;reacting a halogen gas with the alkane halide mixture to form an alkylhalide, an alkyl di halide, an alkyl tri halide, and a hydrogen halidegasses; neutralizing the alkyl di halide, the alkyl tri halide, and thehydrogen halide gasses but not the alkyl halide gas with a suspension ofmagnesium hydroxide; cooling the gasses from the neutralizing step to atemperature to liquefy at least a portion of the gasses to formliquefied gasses; mixing the liquefied gasses with a magnesium benzoateor butyrate solution to form an aqueous solution of benzoate or butyrateethyl esters; separating the benzoate or butyrate ethyl esters in theaqueous solution, which are water insoluble, to form an ester insolublelayer comprising benzoate or butyrate ethyl esters and a water layercomprising water and magnesium halide; contacting the ester insolublelayer comprising benzoate or butyrate ethyl esters with a suspension ofmagnesium hydroxide to form an alcohol.
 10. The method of claim 9wherein the alkane gas is selected from the group consisting of methane,ethane, propane and mixtures thereof.
 11. The method of claim 9 whereinthe halogen gas is selected from the group consisting of chlorine gas,bromine gas, and iodine gas, and mixtures thereof.
 12. The method ofclaim 9 wherein the alkane is methane, the halide gas is selected fromthe group consisting of bromine gas, chlorine gas, and mixtures thereof,and the alcohol is methanol.
 13. The method of claim 9 wherein thealkane is ethane, the halide gas is bromine gas, and the alcohol isethanol.
 14. The method of claim 9 wherein the metal salts of organicacids is selected from the group consisting of magnesium benzoate,magnesium butyrate, or a magnesium salicylate.
 15. The method of claim 9wherein the acids are selected from the group consisting of benzoicacid, butyric acid, and salicyclic acid.
 16. The method of claim 9wherein the alcohol is selected from the group consisting of methanol orethanol.
 17. A method of making alcohol comprising the steps of:reacting, in a fluo solids reactor, solids comprising a metal and ahalogen forming a halogen gas and a metal oxide; condensing the halogengas to form a liquid halogen and a gas comprising trace halogen; feedingthe liquid halogen to a brominator; recovering the trace halogen fromthe gas by absorbing the trace halogen in water and extracting the tracehalogen from the water with an alkane forming an alkane halide;absorbing the trace halogen from the gas comprising trace halogen withwater; feeding the alkane halide to the brominator; reacting, in thebrominator, the halogen and the alkane to form halogenated alkanes;reacting the metal oxide, formed in fluo solids reactor, with waterforming a metal hydroxide; neutralizing at least a portion of thehalogenated alkanes with the metal hydroxide, forming neutralized gassesand liquids; feeding the neutralized liquids to the fluo solids reactor;condensing a portion of the neutralized gasses and feeding the gasportion to the brominator; feeding the liquid portion of the condensedneutralized gasses to an intensive mixer; mixing the liquid portion ofthe condensed neutralized gasses with metal benzoate or butyrate, fedfrom a distiller/reactor, and reacting, forming a reacted liquid;decanting the reacted liquid into a first liquid phase and a secondliquid phase; feeding the first liquid phase, comprising a metal halogenand water, to the fluo solids reactor; distilling and reacting thesecond liquid phase, in the distiller/reactor, removing alcoholtherefrom; and feeding the metal benzoate or butyrate, from thedistiller/reactor, to the intensive mixer.
 18. The method of claim 17wherein the metal salts of organic acids is selected from the groupconsisting of magnesium benzoate, magnesium butyrate, or a magnesiumsalicylate.
 19. The method of claim 17 wherein the acids are selectedfrom the group consisting of benzoic acid, butyric acid, and salicyclicacid.
 20. The method of claim 17 wherein the alcohol is selected fromthe group consisting of methanol or ethanol.